Effect of molecular weight on high-speed melt spinning of nylon 6

An extensive experimental study of the structure and properties developed in as-spun nylon 6 filaments is reported. Five polymers representing different molecular weights in the range 25,000–73,000 g/mol (viscosity average) were studied. These polymers were melt spun over a range of spinning speeds using an air drag type of drawdown device. Maximum take-up velocities achieved were in the neighborhood of 4000 m/min. The structure and properties of the as-spun filaments were characterized using density, DSC, WAXS, SAXS, birefringence, and tensile tests. The structural characteristics and properties of the filaments are strongly dependent on molecular weight. Generally, higher molecular weight leads to higher modulus and filament tenacity and lower elongation to break in the as-spun filaments. The structural changes with molecular weight are rather complicated; the complications are explained in terms of changes of crystallization rate and attainable crystallinity.     

卧式一步法丙纶高强丝生产工艺研究

在意大利ＦＡＲＥ公司卧式一步法丙纶高强丝设备上，研究了聚丙烯熔融指数与丙纶高强丝强度的关系。探讨了纺丝温度、冷却条件、单丝纤度、拉伸倍数等主要工艺条件对丙纶高强丝强度的影响。     

The influence of isotacticity,ethylene comonomer content,and nucleating agent additions on the structure and properties of melt-spun isotactic polypropylene filaments

The influence of isotacticity, ethylene comonomer content, and nucleating agent additions on the structure and properties of melt-spun polypropylene filaments was studied for a series of polypropylenes having similar resin melt flow rates (MFR ≌ 35), average molecular weights, and polydispersities. In general, increasing the degree of isotacticity increases crystallinity and tensile modulus of the spun filaments, while increasing the copolymer content has the opposite effect. Nucleating agent additions also lead to greater crystallinity, but, under certain conditions, the addition of a nucleating agent can lead to lower tensile modulus in spite of higher crystallinity. For given spinning conditions, the tensile strength increased slightly with increased copolymer content but was little affected by tacticity in the range studied. Nucleating agent additions lowered the tensile strength of spun filaments. The effects of nucleating agents on the filament modulus and tensile strength were traced to their ability to raise the crystallization temperature and reduce the level of molecular orientation generated in the filaments. The reasons for the observed behavior are discussed. © 1996 John Wiley & Sons, Inc.     

Effect of hot drawing on properties of wet‐spun poly(L,D‐lactide) copolymer multifilament fibers

Polylactide stereocopolymer multifilament fibers were prepared by wet spinning and subsequent hot drawing. The stereocopolymers were poly‐(L,D ‐lactide) [P(L,D )LA], L/D ratio 96/4, and poly‐(L,DL ‐lactide) [P(L,DL )LA], L/DL ratio 70/30. They were dissolved in dichloromethane and coagulated in a spin bath containing ethanol. The hot‐drawing temperature was 65°C. The draw ratios (DR) were upto 4.5 to the P(L,D )LA 96/4 filaments and upto 3 to the P(L,DL )LA 70/30 filaments. Wet spinning decreased crystallinities of both copolymers. Hot drawing increased the crystallinity of the P(L,D )LA 96/4 filament but not to the level of the original copolymer, whereas the as‐spun and the hot‐drawn P(L,DL )LA 70/30 filaments were amorphous. The filament diameter, tenacity, Young's modulus, and elongation at break were dependent on the DR. The maximum tenacity (285 MPa) and Young's modulus (2.0 GPa) were achieved with the P(L,D )LA 96/4 filament at the DR of 4.5. Respectively, the maximum tenacity of the hot‐drawn P(L,DL )LA 70/30 filament was 175 MPa and Young's modulus 1.3 GPa at the DR of 3. Hot drawing slowed down in vitro degradation rate of both stereocopolymer filaments. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Processing,structure, and mechanical properties of as‐spun polypropylene filaments—A systematic approach using factorial design and statistical analysis

Polypropylene filaments spun under a factorial experimental design were characterized with respect to filament tenacity, elongation, and specific secant modulus. These quantities were assessed quantitatively as responses to seven selected processing parameters using standard statistical methods. It was found that among all the significant factors identified, the draw‐down ratio, which combines metering pump speed (MPS) and filament winding speed (WS), exerts the most significant effects on all the three responses. The grade of polypropylene used, as denoted by its melt flow index (MFI), also significantly influences tenacity and modulus. Spinning temperature, too, influences modulus. In addition, the significant influence of two interaction effects, MPS*WS and MFI*WS, is demonstrated. A further feature of the study is systematic correlation of physical properties with microscopic structure as well as processing conditions. The study has demonstrated that the statistical approach to the development of fiber process technology has the advantages of a one‐step overall design, considerably reduced experimental size, and systematic analysis leading to concise models with known levels of confidence. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 144–154, 2005     

Preparation and properties of polyphenylene-1,3,4-oxadiazole fibres

Copolymers of terephthalic and isophthalic acid (CPODZ) in 1:1 and 3:1 molar ratios with hydrazine sulphate and concentrated sulphuric acid were wet spun using water and H₂SO₄ coagulation baths. The filaments spun into water bath have inferior mechanical properties than those spun in H₂SO₄ bath. Physical properties, namely tenacity, elongation, modulus, resilience, elastic recovery, and dynamic mechanical properties were investigated. 1:1 CPODZ filaments showed higher strength, modulus and elasticity than 1:3 CPODZ filaments. These CPODZ fibres had a higher dynaic modulus and low loss tangent. The density and moisture regain of CPODZ filaments were also determined. The density of 1:1 CPODZ filaments was higher. The filaments spun in water bath had higher moisture regain. 1:1 CPODZ filaments had less regain compared to 1:3 CPODZ filaments.     

Melt‐blowing thermoplastic polyurethane and polyether‐block‐amide elastomers: Effect of processing conditions and crystallization on web properties

Melt‐blown webs from ester and ether thermoplastic polyurethanes and polyether‐block‐amide (PEBA) elastomers were produced at different die‐to‐collector distances (DCD) to study the correlation between the polymer type and hardness, melt‐blowing process conditions, and web properties. An experimental set up was built to measure the air temperature and velocity profiles below and across the melt‐blowing die to correlate the fiber formation process and polymer crystallization behavior to process conditions and web properties. It was shown that air temperature and velocity profiles follow similar trends with increasing distance below the melt‐blowing die: both drop rapidly until reaching a plateau region approximately 5–6 cm below the die. Thereafter, they remain relatively constant with further increasing distance. It was found that crystallization onset and peak temperatures of all block copolymers in this study fall within this region of rapid velocity and temperature drop. This suggests that the polymers have already started to crystallize and solidify before reaching the collector, the extent of which depends on the crystallization kinetics of the polymer. The strong influence of the crystallization kinetics on web strength was clearly demonstrated in the PEBA series. In particular, the hardest grade produced the lowest web strength mainly because of its high crystallization rate and crystallization onset temperature. It is concluded that the melt‐blown web strength is strongly dependent on the degree of fiber‐to‐fiber adhesion within the web, which is determined by the amount of fiber solidification that occurs prior to the collector. The crystallization kinetics of the polymer and the distances traveled between the die and collector or the exposure time of the polymer melt to process and ambient air were shown to be critical in the amount of fiber solidification attained. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

染色条件对聚对苯二甲酸丙二酯纤维性能的影响

研究了染色条件对聚对苯二甲酸丙二酯(PTT)纤维上染率、纤维截面直径、力学性能和回弹性能的影响。结果表明:由于染料分子对纤维的膨润作用,使得纤维染色后截面直径增大,截面形状的圆整度提高,重量明显增大;使纤维的线密度增大,断裂强度降低,而初始模量、断裂伸长率和断裂比功变化的规律性不强。染色对于PTT纤维的拉伸回弹性有明显的影响,但对于其弯曲回弹性影响并不大。随着染色温度的提高,纤维的拉伸回弹率有所提高,而弯曲回弹率有所降低;但染色时间对拉伸和弯曲回弹率基本没有影响。     

The effect of process parameters on the properties of elastic melt blown nonwovens: Air pressure and DCD

An elastic masterbatch and elastic melt blown nonwovens are prepared based successively on styrene-ethylene/butylene-styrene (SEBS) and polypropylene (PP) blend. The phase separation morphology, rheological properties and crystal structure of the elastic masterbatch are investigated. The results show that a compatible and stable structure is obtained in molten SEBS and PP blend with excellent mobility in the temperature range of 210–230°C. The crystallization of PP slows down resulting in a finer structure due to the restriction of the SEBS network structure with rarely change of crystalline structure. The relationship between process parameters and properties of the elastic nonwoven is also studied in detail. Air pressure and die to collector distance (DCD) have discernible effects on fiber diameter and bonding between fibers, further influencing the performances of nonwovens including porosity, tensile strength and elastic recovery. Elastic recovery is shown to be significantly more affected by DCD than by air pressure.     

Melt spinning and drawing of 2‐methyl‐1,3‐propanediol‐substituted poly(ethylene terephthalate)

The structure and properties of fibers prepared from copolymers of poly(ethylene terephthalate) (PET) in which 2‐methyl‐1,3‐propanediol (MPDiol® Glycol is a registered trademark of Lyondell Chemical Company) at 4, 7, 10, and 25 mol% was substituted for ethylene glycol were studied and compared with those of PET homopolymer. Filaments were melt spun over a range of spinning conditions, and some filaments that were spun at relatively low spinning speeds were subjected to hot drawing. The filaments were characterized by measurements of birefringence, differential scanning calorimetry (DSC) crystallinity, melting point, glass transition temperature, wide‐angle X‐ray diffraction patterns, boiling water shrinkage, tenacity, and elongation to break. Filaments containing 25 mol% MPDiol did not crystallize in the spinline at any spinning speed investigated, whereas the other resins did crystallize in the spinline at high spinning speeds. However, compared with PET homopolymer, increasing substitution of MPDiol reduced the rate at which the crystallinity of the melt spun filaments increased with spinning speed and reduced the ultimate crystallinity that could be achieved by high‐speed spinning. The rate of development of molecular orientation, as measured by birefringence, also decreased somewhat with increasing MPDiol content. Shrinkage in boiling water decreased at high spinning speeds as the amount of crystallinity increased; however, the shrinkage decreased more slowly with increase in spinning speed as MPDiol content increased. Tenacity also decreased slightly at any given spinning speed as MPDiol content increased, but there was no significant effect on elongation to break. The addition of MPDiol in amounts up to 7 mol% increased the maximum take‐up velocity that could be achieved at a given mass throughput. This result indicates that the use of higher spinning speeds could potentially increase the productivity of melt spun yarns. Copolymer filaments spun at low speeds were readily drawn to produce highly oriented fibers with slightly less birefringence, crystallinity, and tenacity than similarly processed PET homopolymer. Preliminary dyeing experiments showed that the incorporation of MPDiol improved the dyeability of the filaments. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2598–2606, 2003     

Dynamics of air drawing in the melt blowing of nonwovens from isotactic polypropylene by computer modeling

The dynamics of stationary air drawing in the melt blowing of nonwovens were determined on the basis of a single‐filament model in a thin‐filament approximation that accounts for polymer viscoelasticity, heat of viscous friction in the polymer bulk, and surface energy. Predetermined distributions of the air velocity and temperature along the melt blowing axis were assumed. Axial profiles of the polymer velocity, temperature, elongation rate, filament diameter, tensile stress, and extrapressure were computed for the melt blowing of isotactic polypropylene. The effects of the air‐jet velocity, die‐to‐collector distance, and polymer molecular weight are discussed. We predicted that the filament attenuation and velocity at the collector located in the air‐drawing zone would increase with increasing die‐to‐collector distance. The air‐drawing zone was shorter for higher air velocities and lower molecular weights. No online crystallization was predicted before the achievement of the collector, and melt bonding of the filament in the web should have occurred during cooling on the collector, accompanied by spherulitic crystallization. Significant online extrapressure in the filament was predicted in the case of supersonic air jets as resulting from polymer viscoelasticity, which could have led to longitudinal splitting of the polymer into subfilaments. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Controlling of threadline dynamics via a novel method to develop ultra‐high performance polypropylene filaments

A detailed study was conducted to investigate the effects of horizontal isothermal bath (hIB) on the production of ultra‐high performance polypropylene filaments. Two different commercial PP polymers were used with the melt flow rate of 4.1 and 36 g/10 min. The optimum process conditions depended on polymer molecular weight. Fibers showed distinct precursor morphology for each at each optimum process condition. However, two sets of filaments demonstrated similar fiber tenacity and modulus of about 7 and 75 g d^?1, respectively, for as‐spun and more than 12 g d^?1 for tenacity and more than 190 g d^?1 for modulus values of drawn fibers after just 1.49 draw ratio. The mean value for the modulus after the drawing process for the high melt flow rate was 196 g d^?1. The theoretical modulus of PP is 35–42 GPa¹⁹, (275–330 g d^?1), shows the hIB fiber's modulus performance is approaching its theoretical maximum value. Fibers had greatly improved thermal properties, degree of crystallinity, crystalline and amorphous orientation factors. The hIB spinning system produced highly oriented and predominantly amorphous structure for as‐spun fibers and a well‐defined, highly oriented crystalline fibrillar and amorphous structure after drawing process with the draw ratios lower than 1.5. POLYM. ENG. SCI., 55:327–339, 2015. © 2014 Society of Plastics Engineers     

High modulus/tenacity filaments from blends of different molecular weights of polypropylene

Polypropylene (PP) filaments are prepared by blending two different molecular weight components of PP. A melt‐spinning process to produce filaments includes mixing of components, extrusion, and two‐stage drawing, followed by a unique Gradient Drawing? process. Blending results in highly deformable as‐spun filaments with high draw ratios. For 90:10 blends of PP samples with melt flow indexes of 35 and 3, a high level of crystallinity and crystalline and amorphous orientations are obtained. A sonic modulus of 28 GPa, dynamic modulus of 20 GPa, tensile modulus of 16 GPa, and tenacity of 667 MPa are achieved. These samples are dimensionally stable up to ～100°C. All steps in the production of the filaments are continuous. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1021–1028, 2005     

Application of neural networks to meltblown process control

Process modeling is essential for the control of optimization and an on-line prediction is very useful for process monitoring and quality control. Up to now, no satisfactory methods have been found to model an industrial meltblown process since it is of highly dimensional and nonlinear complexity. In this article, back-propagation neural networks (BPNNs) were investigated for modeling the meltblown process and on-line predicting the product specifications such as fiber diameter and web thickness. The feasibility of this application was successfully demonstrated by agreement of the prediction results from the BPNN to the actual measurements of a practical case. The network inputs included extruder temperature, die temperature, melt flow rate, air temperature at die, air pressure at die, and die-to-collector distance (DCD). The output of the fiber diameter was obtained by neural computing. The network training was based on 160 sets of the training samples and the trained network was tested with 70 sets of test samples which were different from the training data. This research is preliminary and of industrial significance and especially valuable for the optimal control of advanced meltblown processes. © 1996 John Wiley & Sons, Inc.     

聚丙烯腈熔融纺丝技术进展

叙述了聚丙烯腈的结构特征，丙烯腈聚合物的增塑，增塑和非增塑聚丙烯腈熔融纺丝工艺和纤维性质。熔纺制得的聚丙烯腈纤维，适用于纺织、地毯以及用作碳纤维原丝。增塑熔融纺丝技术已达到相当高的水平，熔纺纤维的形态与普通聚丙烯腈纤维类似，但存在皮芯结构，芯部有微孔。制得的聚丙烯腈基碳纤维原丝，拉伸强度达５．５～６．６ｃＮ／ｄｔｅｘ，用这种原丝生产的碳纤维的拉伸强度约为３．６×１０３ＭＰａ，模量约为２．３３×１０５ＭＰａ，伸长率约为１．５％，可制得性能优良的航空航天用复合材料。非增塑熔融纺丝，采用特定的丙烯腈聚合物和纺丝条件，不添加任何增塑剂，用普通熔融纺丝机在１０００ｍ／ｍｉｎ或２０００ｍ／ｍｉｎ以上的速度纺丝，经拉伸可得强度２．２～１１ｃＮ／ｄｔｅｘ、伸长率５％～３０％和模量５５～２２２ｃＮ／ｄｔｅｘ的纤维。     

扁平形聚酯纤维结构和性能研究

对扁平形聚酯纤维和圆形聚酯纤维的结构和性能进行了研究。结果表明 ,扁平形初生丝的双折射比圆形丝大 ;扁平丝的比表面积、沸水收缩率和功系数都比圆形丝大 ,而其杨氏模量和断裂强伸度却比圆形丝小 ,以致使扁平形聚酯纤维具有更好的干爽感和柔韧性     

Effect of initial take-up speed on properties and structure of as-spun and drawn/heat-set poly(ethylene terephthalate) filaments

The effect of initial take-up speed on the properties and structure of both as-spun and drawn/heat-set poly(ethylene terephthalate) filaments was characterized through measurements of birefringence, percent crystallinity, tensile properties, high temperature shrinkage, loss tangent temperature dependence, DSC melting behavior, and wide-angle (WAXS) and small-angle X-ray scattering (SAXS). While a steady trend toward improved as-spun filament orientation and tensile properties occurred with increasing initial take-up speed, the reduced drawability of these more structured precursor filaments resulted in corresponding drawn/heat-set filaments that were of relatively lower overall orientation and tensile strength. The observed trends in tenacity, initial modulus, and high temperature shrinkage of the drawn/heat-set filaments appeared to be well correlated with the extent and distribution of amorphous phase rigidity as perceived through inferences made from the loss tangent temperature dependence. The WAXS patterns of the drawn/heat-set samples indicated that these filaments all possess a well-developed and highly oriented crystalline structure. Application of a simple two phase model allowed the determination of an amorphous orientation factor, which for the drawn/heat-set filaments was generally found to decrease as the draw ratio imposed in order to achieve comparable levels of elongation to break decreased. The SAXS patterns of the drawn/heat-set filaments indicated that comparable long period spacings exist in all cases and that a transition from a four-point pattern to a two-point bar-shaped pattern occurred when the precursor filament possessed some significant amount of as-spun crystallinity. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 2115–2131, 1998     

Mechanical testing of hydroxyapatite filaments for tissue scaffolds preparation by fused deposition of ceramics

Composite filaments with diameter ∼1.75 mm suitable for fused deposition of ceramics were prepared from commercial hydroxyapatite powders (HAp-0, d₅₀ ≤ 35 μm and HAp-1, d₅₀ ≤ 16 μm) and thermoplastic polymer - polyvinyl alcohol. The filament printability in FDC applicable as specific bone-part replacements, is connected to its mechanical strength and slenderness ratio affecting the resistance to buckling. The HAp content in prepared composite filaments was at the level of ∼ 50 % and their mechanical properties were compared to commercial filament based on polylactic acid and ∼ 27 % of gypsite used as inorganic filler. The tensile strength of laboratory prepared filaments was about 3 times lower than strength found for commercial filament. The critical buckling pressure calculated from Euler buckling analysis using measured intrinsic Young´s modulus revealed underestimated critical pressure values ∼ 2.5–5.0 times if compared to values of maximal filament compressive pressure loads simulating buckling.     

Physical and thermal characterization of polylactic acid meltblown nonwovens

A series of polylactic acid (PLA) nonwovens were prepared by the melt blowing process using micro and nano dies. The nonwovens were characterized for structural, thermal, and mechanical properties. These properties varied with the type of die, airflow, and die to collector distance (DCD). The mean pore size for PLA microfiber ranged between 1.82 and 10.48 micrometers, and nanofiber nonwovens ranged between 452 and 818 nanometers. The tensile modulus and strength of PLA nonwovens increased with airflow at a given DCD, but decreased with increased DCD for a given airflow. Thermograms from calorimetry showed microfiber mats had a larger composition of beta‐form crystals than the nanofiber mats. The results showed that a wide range of nonwovens can easily be generated with properties tailored to the specific application. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40593.     

Fabrication of large diameter SiC monofilaments by polymer route

We demonstrate the possibility to fabricate SiC monofilaments with large diameters of 100 μm by a polymer route using a dry-spinning process. The properties of the spinning solution and the parameters of the spinning process were optimized to achieve a circular cross section of the spun filaments despite their large diameter. The evolution of the diameter and the mechanical properties of the filaments with pyrolysis temperature were studied. Filament shrinkage started above 400 °C. A radial shrinkage of about 25% was measured for pyrolysis temperatures of 1200 °C. The mechanical properties significantly start to increase at pyrolysis temperatures above 600 °C. At a diameter of 100 μm the filaments show a tensile strength of 620 MPa and a tensile modulus of 138 GPa after pyrolysis at 1200 °C. A decrease in the filament diameter leads to an improvement of the mechanical properties. We demonstrate the fabrication of these SiC monofilaments on spools.